Disazo dyestuffs



United States Patent Gffice m ffififfllf,

cals with 1-4 carbon atoms, which may be substituted. 3,467,643 Thefollowing radicals A can be used, for example: Walter Ho t L C P g d Ed(1) Aliphatic radicals which may be interrupted by siege g i fi 8351 ggrk :2 ii: hetero atoms or optionally substituted aromatic radicalsfabriken Bayer Akfiengeszilschagfi, Leverkusen, 5 (the latter are alsomentioned as araliphatic radicals), Germany, a corporation of GermanySuch as No Drawing. Filed July 19, 1966, Ser. No. 566,210 CH2CH2,-CHtCH,-CH --CH2CH Claims priority, application Germany, Jan. 14, 1966,

U.S. Cl. 260160 Claims 1 -on2--orn, Ho@-om-om- ABSTRACT OF THEDISCLOSURE 3 A dyestuffs which are free from sulphonic acid groups 15and which correspond to The formula: W

i R CH3 or)", if

0 2 -mo--om-, -1-no- -01-n- I NO in which R denotes a member selectedfrom the class con- CH3 sisting of hydrogen, identical or differentalkyl, aralkyl,

carbocyclic and heterocyclic radicals; R stands for radicals selectedfrom the group consisting of alkyl, aryl, carb- CH2 HC Cm Cm 0malkoxyand carbonamido groups; X stands for substituents; (IIHP m stands for aninteger from 0 to 3; and A represents a member taken from the classconsisting of aliphatic, carbo- 7' cyclic and heterocyclic radicals.

The object of the present invention is to provide valuable 3 new azodyestuffs which are free from sulphonic acid H C-SO2OH groups andcorrespond to the general formula O O a H 40 o c N N II ll 0 O in whichR denotes hydrogen or identical or different, optionally substitutedalkyl, aralkyl, carbocyclic or heterocyclic radicals, R representsalkyl, aryl, carbalkoxy and -H o- -o H=CH CH carbamido radicals, theradicals X are identical or different 2 Q Q 2 substi'tuenis, m siandsforintegeis'ffom 0 t0 3, af ld A i (2) Carbocyclic (saturated orunsaturated) radicals an allphatlc, arallphatlc, carbocychc hete'rocychcTad! which in the case of polynuclear radicals may also be interthedyestuffs are free from sulphonlc acld groups; the rupted byheterocyclic radicals or may contain fused above-mentioned alkyl, aryl,carbamido, aliphatic, aralir5 h li radicals Such as phatic, carbocyclicand heterocyclic radicals, however, may contain non-ionic substituents.

The radicals R can be monoor polynuclear; radicals of the benzene andnaphthalene series are preferred. The fol- 1 C1 lowing radicals may bementioned in this context, for ext I ample: phenyl-; 2- or 3- or4-methylphenyl-1; 2- or 3- or 4-chlorophenyl-1, 2- or 3- or4-methoxy-phenyl-1; 3-nitr0- phenyl 1; 3 sulphonamidophenyl 1;2-methyl-4-chlorophenyl-1; 2,4-dimethylphenyl-l and naphthyl-l or -2;2,6- dichloroor -dimethylor 2-chloro-6-methylphenyl-1. r

Suitable substituents X are, for example; lower alkyl substituents, suchas methyl and ethyl; chloro and nitro sub- H8O CH3 0cm OCH; stituents;lower alkoxy substituents, such as methoxy and (3H3 N02 (3H3 ethoxy;fiuoro, bromo, methylsulphonyl, ethylsulphonyl, phenylsulphonyl,trifiuoromethyl substituents; and carbalk- 1 oxy substituents, such ascarbomethoxy and carbethoxy-t Preferred alkyl radicals R and R are loweralkyl radi- ('31 (ill C1 (31 l l c1 c1 c1 (3) Heterocyclic radicals,such as 4 A group of especially valuable dyestuffs in the range of theproducts of the Formula I corresponds to the formula R H- N=N (H) 011 \N\NHA R:

R4 R; 2 (In) in which R stands for methyl, carbomethoxy or carbethoxysubstituents, R for hydrogen, or for methyl, nitro, chloro, methoxy,ethoxy, sulphonamido substituents, R for hydrogen or for methyl, chloro,methoxy substituents, R for hydrogen or a chloro substituent, and A foran aliphatic, araliphatic, carbocyclic or heterocyclic radical; thedyestuffs are free from sulphonic acid groups.

The new azo dyestuffs (I) and (Ia) are obtained, when azo compounds ofthe formula wa F in which R, R R R R X and n1 have the same meaning asabove, or functional derivatives of these azo-dicarboxylic acids,especially the monoor diesters, monoor diamides, dicarbonimides oranhydrides, are reacted with diamines of the general formula in which Ahas the same meaning as above, in a molar ratio of components (II) or(11a) to component (III) of approximately 2:1, in the presence of acidiccondensation agents, the components being so chosen that the finaldyestuffs are free from sulphonic acid groups.

The reaction of the starting components is preferably carried out in ahigh-boiling organic solvent or solvent mixture, and the components canalso serve as organic solvents. The condensation takes place at anelevated temperature, generally in the range from to 240 C., preferablybetween C. and 180 C.

The monoazo compounds of the general Formula II and 11a are prepared inthe usual manner by diazotising optionally substituted 3-amino-phthalicacids or their functional derivatives and coupling with suitablepyrazolones, the components being free from sulphonic acid groups.

The following diazo components can be used, for example, for thepreparation of the azo compounds (II) and (Ila) 3-amino-phthalic acid;3-amino-phthalic acid-mono and diesters such as 3-amino-phthalic acidmonomethyl ester-( 1) or 3-amino-phthalic acid dimethyl ester;3-aminophthalimide; 3-amino-6-methyl-phthalic acid; 3-amino-5-methyl-phthalic acid; 3-amino-4-methyl-phthalic acid; 3 aminoS-nitro-phthalic acid; 3-arnino-6-nitro-phthalic acid;3-amino-S-methoxy-phthalic acid; 3-amino-6-methoxy-phthalic acid;3-amino-6-chloro-phthalic acid; 3-amino-4-methoXy-phthalic acid;3-amino-6-bromo-phthalic acid; 3-amino-6-fluoro-phthalic acid;3-amino-5,6-dimeth- 5 oXy-phthalic acid;3-amino-4,5,6-trimethoxy-phthalic acid;3-amino-5,6-methylene-dioxy-phthalic acid;

ITIH:

I COOH C0011 3 amino 5 cyano phthalic acid; 3 amino 6 cyanophthalicacid; 3-amino-5-methoxy-6-ethoxy-phthalic acid; 3 amino 6methyl-sulphonyl-phthalic acid; 3-arnino- '6-trifiuoromeIhyl-phthalicacid; 3-amino-5-carbethoxyphthalic acid; 3-amino-6-carbethoxy-phthalicacid.

The following pyrazolone coupling components can be used, for example,for synthetising the monoazo compounds (II) and (11a);3-methyl-pyrazolone-(5); pyrazolone'-(5)-carboxylic acid-(3)-ethylester; 1,3-dimethylpyrazolone-(S); 1-benzyl-3-methyl-pyrazolone-(5);1-(2'- benzothiazolyl) 3 methyl-pyrazolone-(S); l-[fl-(carbaminophenyl-hydroxyethyl] -3-methyl-pyrazolone- 5) of the formula 1-(fl-benzoylamino-ethyl -3-methyl-pyrazolone-(5 1- (4-chloro-phenyl-3-methyl-pyrazolone- 5) l- 4'-methylphenyl) -3-methyl-pyrazolone- 5) l-3 -nitrophenyl -3-methyl-pyrazolone- 5) 1- 3'-sulphonamidophenyl-3-methyl-pyrazolone- (5);

l-phenyl-3-methyl-pyrazolone- (5 3-methyl-pyrazolone-(5 1-2-chlorophenyl- -3-methyl-pyrazolone- 5) 1- 3'-chlorophenyl--3-methyl-pyrazolone- 5);

1- 2',5 '-dichlorophenyl -3 -methyl-pyrazolone- 5);

1- 4-nitro-phenyl) -3-methyl-pyrazolone- 5) 1- (3 -carbomethoxyphenyl -3-methyl-pyrazolone- 5) l-phenyl-pyrazolone- 5 -carboxylic acid- 3-anilide;

l-phenyl-pyrazolone-(S -carboxylic acid-(3 )-ethyl ester;

l-phenyl-pyrazolone- 5 -carboxylic acid- 3 -amide;

1- 3 '-nitrophenyl- -pyrazolone- 5 -carboxylic acid- (3 ethyl ester;

1- 4'-nitrophenyl- -pyrazol0ne- 5 -carboxylic acid- 3 ethyl ester;

1-phenyl-pyrazolone-(5)-carboxylic acid- 3 )-methyl ester The followingaliphatic, araliphatic, carbocyclic and heterocyclic diamines are used,for example, for the condensation of the monoazo compounds (II) or (Ila)with the diamines (III), which is carried out according to the inventionin high-boiling organic solvents with the addition of acidiccondensation agents:

1,2-diamino-ethane;

l ,4-diaminobutane;

1,6-diamino-hexane;

1,4-diaminomethyl -benzene;

N,N-bis- 3-amino-n-propyl -methylamine; 3,3'-diarnino-n-propyl ether;1,4-diamino-benzene; l,4-diamino-2-chloro-benzene;l,4-diamino-3-methyl-benzene; 1,4-diamino-2,5-dimethyl-benzene;1,4-diamino-Z-nitro-benzene;

2-methyl-5 -methoxy-1,4-diamino-benzene2,5-diethoxy-1,4-diamino-benzene; 1,3-diamino-benzene;2,3,5,6-tetrachloro-1,4-diamino-benzene;2,4,5,6-tetrachloro-1,3-diamino-benzene; 4,4'-diamino-diphenyl;

6 2,2-dichlo1'0-4,4'-diamino-diphenyl; 3 ,3'-dichloro-4,4-diamino-diphenyl; 3 ,3 '-dimethoxy-4,4-diamino-diphenyl;2-nitro-4,4-diamino-diphenyl; 3 ,3 '-diet-hoxy-4,4'-diamino-diphenyl; 3-methyl-4,4'-diamino-diphenyl; 3 ,3 '-dimethyl-4,4-diamino-diphenyl; 3,3 -dimethyl-4,4-diamino-6,6-dinitro-diphenyl;2,2-dimethyl-4,4-diamino-diphenyl; 2,2-dichloro-4,4-diamino-5 ,5'-dimethoxy-di phenyl 2,2',5 ,5 '-tetrachloro-4,4'-diamino-diphenyl; 3,3',5,5-tetrachloro-4,4-diamino-diphenyl;3,3,5,5'-tetramethyl-4,4-diamino-diphenyl;perch1oro-4,4-diamino-diphenyl; 4,4f-diamino-diphenyl-ether;4,4--diamino-diphenylsulphone; 3 ,3'-diamino-4,4'-dichloro-diphenylsulphone; 3,3'-diamino-4,4-dimethoxy-diphenylsulphone; 4,4f diamino-diphenylketone;3 ,3'-diamino-diphenylketone; 3,3'-diamino-4,4'-dichloro diphenylketone;3 ,3 -diamino-4,4'-dimethoxy-diphenylketone;4,4'-diamino-diphenylmethane; 3, 3 '-diamino-diphenylmethane;4,4'-diamino-3,3',5,5-tetrachloro-diphenylmethane; 4,4-diamino-stilbene;4,4Gdiamino-benzanilide; 4,4-diamino-diphenyl-ethane (synm) 4,4-diamino-azobenzene; 2,8- diamino-chrysene; 1,4-diamino-naphthalene; l,SdiaminO-naphthaIene; 2,6'diamino-naphthalene; 2,7-diamino-naphthalene;2- 4'-amino-phenyl -5-amino-benzotriazole; 2,5-bis(4-amino-phenyl)-oxdiazo1e; 4,4-diamino-diphenyl urea;4,4';diamino-3,3 '-dimethoxystilbene; 2,6-diamino-benzothiazole;2-(4'-aminophenyl)-6-amino-benzothiazole; 2,7-,diamino-fluorene;2,7-diamino-diphnylene'-oxide; 2, 7-diamino-diphenylene-sulphone; 2,5-bis(4'-amino-phenyl)-thiadiazole; 2,5 -bis 4'-amino phenyl) -triaz0le.

The following solvents boiling above C. may be mentioned, by way ofexample, for the condensation of the monoazo dyestuffs (II) or (Ila)with the diamines (III) in high-boiling organic solvents: benzene,toluene, xylenes, chlorobenzene, 0-, m-, p-dichlorobenzene,trichlorobenzenes, nitrobenzene, quinoline, glacial acetic acid,cyclohexane, 1,2,3,4-tetrahydro-naphthalene, naphthalene,tetrachloroethylene, di-n-butyl ether, anisole, diphenyl ether, decalinand mixtures of such solvents.

Suitable acidic condensation agents are, for example, acetic acid,propionic acid, anhydrous sodium acetate, zinc ,chloride, ferricchloride, aluminium chloride, hydrochloric aicd, sulphuric aid, oxalicacid, formic acid, boron trifluoride and orthophosphoric acid.

Symmetrical and asymmetrical dyestufis of the Formula I can besynthetised, dependent upon the' choice of the component (II).

The products obtained according to the present process are hardlysoluble to insoluble in water. They are valuable pigment dyestuffs theshades of which are in the greenish yellow to yellow range. The pigmentsare usually obtained in crystalline form. They are characterised by agood colour strength, very good thermal stability, and by fastness tosolvents, light, lacquer coating and migration and are therefore usedfor the colouring of plastics, e.g. of polyvinyl chloride containingplasticisers, of lacquers and papers, and for the production of printinginks and pigment pastes.

Because of their excellent thermal stability, the products areespecially suitable for colouring copolymers and grafted polymers ofacrylonitrile-butadiene-styrene. They are stable even at temperatures of200 C. and above.

Belgian patent specification No. 652,251 already mentions pigmentdyestuffs of the general formula CO CO in which K is defined as theradical of any coupling component, A as an aromatic or heterocyclicsystem and R as a bivalent alkyl, aryl, aralkyl or hetero radical.However, this patent specification does not contain a single example ofa dyestufi of the general formula there stated, and not even an exampleof one of the components K, A and R The patent specification otherwisecontains only a few, very general data regarding processes for theproduction of the pigment dyestuffs.

The following examples are given for the purpose of illustrating theinvention; the parts are parts by weight and the temperatures are givenin degrees Centigrade.

EXAMPLE 1 44.5 parts 3-amino-phthalic acid are suspended in 500 partswater, 250 parts ice and 80 parts concentrated hydrochloric acid areadded, and the mixture is diazotised at 0-5 with a solution of 17.1parts sodium nitrite in 50 parts water. The excess nitrite is removed bymeans of amidosulphonic acid.

43 parts 1phenyl-3methyl-pyrazolone-(5) are suspended in 200 partsethanol, 400 parts of a 10% sodium hydroxide solution are added, 250 g.ice are thrown into the mixture and the above diazo suspension is thenintroduced at 5l5. When the coupling is completed, the reaction mixtureis acidified with semi-concentrated hydrochloric acid, the product isfiltered off with suction, washed with water until free from acid, anddried in a drying cabinet at 80. The yield is 85 parts azo dyestutf.

For conversion into the anhydride, these 85 parts azo dyestuff areheated with 500 parts chlorobenzene and 50 parts acetic anhydride atabout 110 for 3-4 hours, the reaction mixture is cooled to roomtemperature, the product is filtered off with suction, washed with lightpetrol and dried. 80 parts monoazo-o-dicarboxylic anhydride are thusobtained, M.P. 286-288".

7 .20 parts of the anhydride and 1.08 parts 1,4-diaminobenzene areheated in a solution of 25 parts glacial acetic acid and 500 partso-dichlorobenzene at 130-140 for 25 hours. The pigment is filtered ofl.with suction at 60- 70", washed with 100 ml o-dichloro-benzene and thendried in a vacuum at 80 until the weight is constant. This method yields7.20 parts of a yellow pigment dyestuff of the formula l If OH l 0EXAMPLE 2 44.5 parts 3-amino-phthalic acid are diazotiscd as in Example1.

70 parts 1-(3' nitrophenyl)3-methyl-pyrazolone (5) are suspended in 200parts ethanol, 400 parts of a 10% sodium hydroxide solution are added,250 parts ice are thrown into the mixture, and coupling is then carriedout at 5l0 by adding the diazo suspension of 3-aminophthalic acid inportions. When the coupling is completed, the reaction mixture isadjusted to pH 1-2 by means of semi-concentrated hydrochloric acid andthe azo dyestutf is filtered off with suction. It is washed with wateruntil free from acid and dried at The yield is 98 parts dyestuff whichis converted into the dicarboxylic anhydride by heating it for 3-4 hoursin 500 parts chlorobenzene with 50 parts acetic anhydride. Yield ofanhydride; 82 parts; M.P. 305.

8.3 parts monoazo-o-dicarboxylic acid are heated in 500 partso-dichloro-benzene with 25 parts acetic acid at for 4 hours. 2.53 parts2,2'-dichloro-4,4'-diamino diphenyl are then added and heating iscontinued at for 25 hours. The reaction mixture is subsequently cooledto 60-70, the precipitated pigment is filtered off with suction, washedwith 100 parts warm o-dichlorobenzene and dried in a vacuum at 80 untilthe weight is constant. 9.5 parts of a yellow pigment dyestuff are thusobtained, which has very good fastness to light and lacquer coating andcorresponds to the following formula:

mo -N= 0 H I 01 r I G v 0 NO:

EXAMPLE 3 44.5 parts 3-amino-phthalic acid are diazotised as in Example1.

50 parts 1-(4'-methylphenyl)3-methyl-pyrazolone-(5) are suspended in 200parts ethanol, a solution of 40 parts caustic soda in 60 parts water isadded, followed by the addition of 200 parts ice, and the diazosuspension is then introduced in portions at 5-10.

When the coupling is completed, the reaction mixture is acidified withsemi-concentrated hydrochloric acid, the dyestuff is filtered off withsuction, washed with water until free from acid, and dried in a dryingcabinet at 80. The dyestutt' yield is 94 parts. By heating the productin 600 parts chlorobenzene with 60 parts acetic anhydride for 4 hours,filtering off with suction and drying, there are obtained 84 parts ofthe dyestuff dicarboxylic anhydride of melting point 294295.

7.4 parts of this monoazo-o-dicarboxylic anhydride are suspended in asolution of 500 parts o-dichloro-benzene and 50 parts acetic acid, 1.16parts hexamethylene-diamine are added and the reaction mixture is heatedat ISO-140 for 25 hours. The pigment is filtered otf with suction at 50and dried in a vacuum at 80. There are thus obtained 7.1 parts of ayellow pigment dyestuff of very good fastness properties and thefollowing formula II C N=N O a I u N-(CHg) Very valuable yellow pigmentdyestuffs are also obtained, when the procedure described in Examplesl-3 is followed, but with the difference that, instead of the diazocomponent, coupling components and diamines there specified, there areused the diazo, coupling and diamine warm o-dichlorobenzene and dried.9.8 parts of pigment components listed in the following table. dyestuffare thus obtained.

Dinzo component Coupling component Diamine 3-amino-phtha1ie acidl-phenyl-3-methyl-pyrazolone-(5) 1,4diamino-butane. Do ..d01,6-diamino-hexane. Do... .i 1,4-di-(aminomethyD-bemene.

4,4'-diamino-diphenyl ether.

3,3'diamino-di-n-propyl other. 2,2-diehloro-4,4'-diamin0-diphenyl.1,4-diamino-butane.

. 1,4-di-(aminomethyl)-benzene. 1,4-diamino-benzene.

4,4-diamino-diphenyl.

. 2,2'-dichloro-4,4-diamin0diphenyl. 3,3-dichloro-4,4-diamino-diphenyl.1,2-diamino-ethane.

.. 1,4diamino-butane.

. 1,6-diamino-hexane.

l. 4,4'-diamino-dipheny1methane. 1,4diamino-benzene.

1,4-diamino-2-chloro-benzene.

3,3'-diamino-di-n-propyl ether. 1,2-diamino-ethane.

1,4-diamino-butane.

. 1,6-diamino-hexane.

. 3,3-diamino-di-n-propyl ether. 1,4-diamino-benzene.

. 1,4-di-(aminomethyl) -benzene. 1,2-diaminoethane, 1,4-diamino-butane.1,6-diamin0-hexane.

. 1,4-diamino-benzene.

.... 4,4-diamino-dipheny1.

3,3-dimethyl-4,4'-dian1ino-diphenyl. ....do 4,4'-diamlno-diphenyl ether.1-(3'-su1phonamidophenyl)-3-methyl-pyrazolone-(5) 1,2-diamino-ethane.

.... do. 1,6-diamino-hexane.

1,4-diamino-benzene.

.. 1,4-diaruino-naphthalene.

2, 7-diamin0-naphthalene.

1,2-diamino-ethane.

. 1,4-diamino-benzene.

1,6diamino-hexane.

. 2,2-dichloro-4,4diamino-dipheny1.

4,4-diarnino-diphenyl ether.

.. 4,4-diamino-stilbene.

1,4-diamin0-benzene 1,4diamino-diphenyl. 1,2-diamino-ethane.1,4-diamino-benzene. 4,4-diamino diphenyl. 1,2-dlamino ethane.1,4-diamino-benzene.

.. 4,4-diamino-dipheny1.

. 1,2diamino-ethane.

. 1,4-diamino-benzene.

4,4'-diamino-diphenyl.

1,2-diaminoethane.

1 ,-diamino-benzene.

. 1,2-diamino-ethane.

1,2-diamino-benzene.

4,4-diamino-diphenyl.

1,2-diamino-ethane.

.... 4,4'-diamino-benzanilide.

. 1,2-diamino-ethane.

. 4,4'-diamino-benzanilide.

Do 0 4,4'-diamino-diphenylsulione.

EXAMPLE 4 EXAMPLE 6 7.9 parts of the dicarboxylic anhydride of thedyestuif 55 7 parts of the anhydride of the azo dyestuif of 3- fromdiazotized 3-amino-phthalic acid and 1-(2-chloroamlnophthalic a d andl-pheny1-3-methyl-pyrazolone-(5) h -3- h l, 1 5 d 08 parts of 1,4- (or7.5 parts of the corresponding dicarboxylic acid) and diamino-benzeneare refluxed for 6 hours in a mixture of ge of L haHc are heated for 8hours at 250 parts of chlorobenzene and parts of glacial acetic 120 In amlxtul'e Of 250 Parts o enzcnc and parts acid. The reaction mixture issubsequently cooled to 70 pljopioniq acid- The Pi p lf g fi t isfiltered off and the precipitated pigment is filtered off with Suction,with suction at 60 to 70 washed with warm nltrobenzenc d dried in avacuum until the Wei ht is constant 6 1 ddr dinavacan g 3:3 1 t l i e iv i ztf f rfst a ht 8 1 parts of a parts of a reddlsh yellow Plgment arethus Obtamed: Whlch g has a very good fastness to light and lacquercoating. greenlsh yellow pigment are thus obtalned, whlch has a What weclaim is: 65 Very good fastness to hght' 1. A20 dyestuffs which are freefrom sulphonic acid EXAMPLE 5 groups and which correspond to theformula:

8.9 parts of the monoazo dyestulf of diazotized 3-amino- R1 N=N f6-chlorophthalic acid and 1-(2-chlorophenyl)-3-methylll J I Cpyrazolone-(S) are heated for 2 hours at in a mix- \N ture of 250 partso-dichloro-benzene and 25 parts glacial acetic acid. 2.27 parts4,4'-diamino-benzanilide are added R and heating is continued for 6hours. The precipitated (X).u pigment is filtered off with suction at60, washed with 7 0 2 in which R is selected from the class consistingof lower alkyl, phenyl, naphthyl radicals, substituted lower alkyl,substituted phenyl and substituted naphthyl radicals wherein thesubstituents are methyl, chloro, methoxy, nitro, or sulphonamido; R isselected from the group consisting of hydrogen, lower alkyl, carboxylicacid methyl ester, carboxylic acid ethyl ester, carboxylic acid amide,carboxylic acid anilide; X is selected from the group consisting oflower alkyl, chloro, fiuoro, bromo, nitro, lower alkoxy, methylsulphonyl, ethyl sulphonyl, trifiuoromethyl, phenyl sulphonyl, andcarbo-lower alkoxy; wherein m stands for an integer from to 3; and A isselected from the class consisting of divalent aliphatic, araliphatic,or carbocyclic hydrocarbon radicals, hetero-atom containing radicalshaving the formulae:

heterocyclic radicals having the formulae:

12 and substituted radicals of said aliphatic, araliphatic, carbocyclic,hetero-atom containing and heterocyclic radicals wherein thesubstituents are nitro, chloro, methoxy or ethoxy.

2. A20 dyestuffs which are free from sulphonic acid groups and whichcorrespond to the formula:

13 14 heterocyclic radicals having the formulae: 7. The azo dyestufi ofthe formula N N N CH CGN=N N OH 8. The azo dyestuff of the formula ICH3-OCN =N N, AN A N t I 00 and substituted radicals of said aliphatic,araliphatic, carbocyclic, hetero-atom containing and heterocyclicradicals wherein the substituents are nitro, chloro, methoxy or ethoxy.

3. A20 dyestufis of claim 2 wherein A is a lower alkyl- The azo dyestufiof the formula ene group, a phenylene group, a dlphenyl group, asubstituted phenyl group or substituted diphenyl group, the

substituents being methyl, nitro, chloro, methoxy, or

l A I GO ethoxy. N

4. The azo dyestuff of the formula N-CHz- "CH (IJ-fiN=N 0 0 10. The azodyestuff of the formula CH3CCN=N u n CO N N 5. The azo dyestuif of theformula FCHs--C-CN=N IUI '21) CO 40 \CO References Cited 2 FOREIGNPATENTS 6. The azo dyestutf of the formula 652,251 12/1964 Belgium CH-o-cN -=N a I H I 00 CHARLES B. PARKER, Primary Examiner CH D. M.PAPUGA, Assistant Examiner \C US. 01. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,467,643 September 16, 1969 Walter Horstmann et al.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 1, line 45, formula, the single bond connecting (X) to the firststructure left-hand side is missing. Column 2, lini l0, "-CH [CH CHshould read -CH (CH CH lines 2 to 30 should read same column 2, lines 60to 70, open valences are missing in the following formulae and shouldread as follows:

OCH OCH N02 CH3 H CO Column 3, lines 5 to 40, open valences are missingin the followi:

formulas and should read as follows:

HSC CH3 same column 3, lines 55 to 65, open valences are missing in thefollowing formulas and should read as follows:

@QDNQ Column 6, line 42, "2,7diamino-diphnyleneoxide" should read2,7-diamino-diphenylene-oxide line 58, "aicd" should read acid "aid"should read acid Column 11, claim 1,

line 55, open valences are missing in the following formulas and shouldread as follows:

Column 12, claim 2, lines 70 to 75, open valen'ces are missing and thefollowing formula should read as follows:

Column 13, claim 2, line 15 should be' changed from Q to Column 14,claim 9, line 30, the ortho'chlorosubstituent is missing in the phenylradical. Column 3, line 45, column 11, line 55, and column 12, line 70,the radical O O m hould read m N N Signed and sealed this 13th day ofOctober 1970.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

